Despite the potentialities of the quantum mechanics (QM)/fluctuating charge (FQ) approach to model the spectral properties of solvated systems, its extensive use has been hampered by the lack of reliable parametrizations of solvents other than water. In this paper, we substantially extend the applicability of QM/FQ to solvating environments of different polarities and hydrogen-bonding capabilities. The reliability and robustness of the approach are demonstrated by challenging the model to simulate solvatochromic shifts of four organic chromophores, which display large shifts when dissolved in apolar, aprotic or polar, protic solvents.

We present a detailed computational study of the UV/Vis spectra of four relevant flavonoids in aqueous solution, namely luteolin, kaempferol, quercetin, and myricetin. The absorption spectra are simulated by exploiting a fully polarizable quantum mechanical (QM)/molecular mechanics (MM) model, based on the fluctuating charge (FQ) force field. Such a model is coupled with configurational sampling obtained by performing classical molecular dynamics (MD) simulations. The calculated QM/FQ spectra are compared with the experiments. We show that an accurate reproduction of the UV/Vis spectra of the selected flavonoids can be obtained by appropriately taking into account the role of configurational sampling, polarization, and hydrogen bonding interactions.

Ethanol and 2,2,2-trifluoroethanol show profoundly different local effects on their solvation shell, revealed via terahertz spectroscopy, molecular dynamics simulations and the random network model.

The photoacid 8-hydroxypyrene-1,3,6-trisulfonate (HPTS) is one of the most widely used fluorescent probes for studying proton transfer and local pH in systems from advanced materials to plants, environmental sensors to medicine. HPTS exists as two different species: the acid and its conjugate base, which lead to unique protonation-state-dependent translocation of the molecule when it is nanoconfined within anionic AOT reverse micelles. Using steady-state and time-resolved optical spectroscopy, molecular simulations, and IR solvation shell spectroscopy, we report that the protonated HPTS species associates strongly with the micelle interface via hydrogen bonding. In contrast, its deprotonated species resides in the micelle’s aqueous interior. Our results show that photoexcitation of the acid species and its subsequent deprotonation leads the conjugate base to rapidly move away from the interface into the water pool. This light-induced translocation, an effect observed for a range of micelle sizes, challenges the prevailing view where molecular probes are assumed to be static reporters of their environments, remaining in a fixed location for the duration of an experiment. This is especially relevant for interpreting results in the numerous studies enlisting optical spectroscopy of HPTS to report on complex systems. Our findings reveal the potential for molecular probes as dynamic explorers capable of mapping environmental heterogeneity on the timescale of the very processes they are designed to measure.